Process and composition for cleaning and imparting water and oil repellency and stain resistance to a substrate

ABSTRACT

Container-stable alkaline cleaning compositions and processes are provided which are effective for cleaning carpets, upholstery and the like, and for imparting water and oil repellency and stain resistance thereto. One such composition comprises in an aqueous medium: detergent, water-dispersible carboxyl-containing material which forms water-insoluble zinc or zirconium salts, a water-dispersible zinc or zirconium coordination complex, a Lewis base, and a fluorochemical compound containing a fluoroaliphatic group and having acid functionality and being capable of imparting water- and oil-repellency to a substrate.

United States Patent 1191 Loudas 1 1 Aug. 26, 1975 PROCESS AND COMPOSITION FOR 3,377,197 4/l968 Erby et a1. 117/121 L I AND IMPARTING WATER AND 3,382,097 5/1968 Erby et a1. ll7/135.5 X OIL REPELLENCY AND STAIN 3,462,294 8/1969 Thomas 106/2 X RESISTANCE TO A SUBSTRATE OTHER C TI NS [75] Inventor: Basil L. Loudas, St. Paul, Minn. Detergents and Emulsifiers" l963 Annual-MC Cutcheon, [nc., p. 157, [TP 990 D4]. [73] Assignee: Minnesota Mining and Manufacturing p y Primary Examiner-S. Leon Bashore Paul Minn- Assistant ExaminerMarc L. Caroff [22] Filed: Man 7, 1973 Attorney, Agent, or FirmAlexander, Sell, Steldt &

DeLal-lunt [21] Appl. No.: 338,935

Related US. Application Data [57] ABSTRACT 3 continuatiomimpan f sen No 122,]43. March 3, Container-stable alkaline cleaning compositions and 197i, b d d, processes are provided which are effective for cleaning carpets, upholstery and the like, and for imparting 52 us. Cl. 134/4; 8/137; lO6/2; water and Oil repellency and Stain resistance thereto- 134/26; 252/89 One such composition comprises in an aqueous me- [51] Int. Cl.*. B08B 7/04; C111) 1/()(); COQK 3/00 dium: detergent, water-dispersible carboxyl-containing [58] Field of S h 134/4 26; 106/2; 8/137; material which forms water-insoluble zinc or zirco- 252/39; 1 17/121 141 nium salts, a water-dispersible zinc or zirconium coordination complex, a Lewis base, and a fluorochemical [56] Ref e Cit d compound containing a fluoroaliphatic group and hav- UNITED STATES PATENTS ing acid funetionality and being capable of imparting 3,308,078 3/1967 Rogers et a1, 260/285 R water and olhepellency to a substrate 3,362,782 l/l968 Gagliardi 8/[37 X 9 Claims, N0 Drawings PROCESS AND COMPOSITION FOR CLEANING AND IMPARTING WATER AND OIL REPELLENCY AND STAIN RESISTANCE TO A SUBSTRATE This application is a continuation-in-part of copending application Ser. No. l22.l43. filed Mar. 8. l97l. now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to cleaning compositions and. more specifically. to treatment with aqueous cleaning compositions to impart water and oil repellency and stain resistance to a substrate during the cleaning operation.

2. Description of the Prior Art The treatment of various textile fabrics with fluorochemicals to impart water and oil repellency has been known to those in the art for several years. It has also been proposed, e.g.. in US. Pat. Nos. 3.068.187; 3.256.230; 3.256.23l; 3.277.039; and 3.503.915. to mix fluorinated polymers with nonfluorinated polymers to obtain a mixture which will impart good water and oil repellency to textiles, paper and leather.

However. such prior art systems are designed for permanent treatment of the substrate and ordinarily there is only one application of the treating composition to the fabric. For example. the textile. carpet. upholstery, etc. may be treated only at the place of manufacture and the treatment is expected to be effective for a considerable length of time. Because it is difficult to treat a textile material which has once been soiled and because of the nature of the treating process. i.e.. heating, drying and curing. it is not generally feasible to re-treat the carpet. upholstery or other material in the same manner as was done initially.

It has also been proposed (U.S. Pat. No. 3.377.l97) to treat previously cleaned textile fabric. leather, rugs. etc. with fluorine-containing organometallic compounds to impart resistance against soiling. staining and wetting. It has been further suggested (U.S. Pat. No. 3.382.097) to impart oil and soil repellency to textile fabric. leather. rugs. etc. by treating with a solution of a certain fluorinated organic carboxylic acid. This reference also suggests combining a detergent with a fluorochemical acid in an aqueous medium for a one-step cleaning and treating operation. However. such a cleaning and treating step does not impart water repellency. Although Netherlands Patent Appln. No. 6.606.734 suggests the dispersing of an insoluble fluorocarbon compound in a laundering composition useful for a two-step cleaning cycle. such disclosure does not provide the one-part cleaning compositions of this invention which are useful in one-step cleaning operations wherein insoluble fluorochemical salts are formed on the substrate to impart water and oil repellency in the presence of detergent residue.

Other prior art cleaning Compositions. e.g.. carpet shampoos. do not impart water and oil repellent properties to a substrate. Rather. many ofsuch conventional cleaning compositions leave hydrophilic and oleophilic residues on the cleaned substrate which actually attract and hold stains. dirt. etc. Although some cleaning compositions contain ingredients designed to impart soiling resistance to a substrate. such compositions do not im part water and oil repellency.

There has not heretofore been described a onepart composition which is useful for both cleaning a substrate and imparting water and oil repellent properties thereto in one operation. Rather. the prior art Compositions are primarily designed for either permanent treating or for cleaning only. not for cleaning and treating. Moreover. such compositions do not impart highly desirable resistance to waterand oil-borne stains and dry soil.

SUMMARY OF THE INVENTION The present invention provides novel compositions and processes for the cleaning and the fluorochemical treatment of carpets. upholstery and the like to impart water and oil repellency and stain resistance thereto. Because the novel compositions contain both detergent and fluorochemical. it is possible to both clean the carpet or other substrate and also impart repellent properties thereto in one operation.

In accordance with the invention. there is provided a container-stable, water-dilutable alkaline cleaning composition which. in one embodiment. comprises in an aqueous medium:

a. one part by weight of at least one water-dispersible detergent which is capable of drying to a non-oily. non-tacky residue.

b. up to about 6.5 parts by weight of at least one water-dispersible organic carboxyl-containing material selected from the group consisting of:

i. water-dispersible mono-carboxylic acids having eight carbons or more. or alkali metal or ammonium salts thereof. and

ii. watendispersible alkali metal or ammonium salts of polymers containing poly-carboxylic-acid functionality. said polymers having at least three carbons in the backbone chain per carboxyl group;

said carboxyl-containing material being free of fluoroaliphatic radicals and being capable of forming solid. hydrophobic. water-insoluble zinc and zirconium salts below about pH 8.

c. at least one water-dispersible Lewis base present in an amount sufficient to temporarily maintain said composition about pH 8 when said composition is exposed to the atmosphere under conditions of use.

d. at least one zinc or zirconium coordination complex which is waterdispersible above about pH 8 and which provides sufficient zinc or zirconium ions below about pH 8 which are capable of combining with substantially all of the acidic radicals present in said composition, and

c. up to about l.5 parts by weight of at least one fluorochemical compound having acid functionality. said fluorochemical compound having the formula: (R/)"X(A)n, where R, is a fluoroaliphatic radical. u is an integer of l or more. X is a linking group having a valence of a plus I) and being less electronegative than a CF group. A is an acid group. and b is an integer of l or more. said fluorochemical compound being capable of imparting water and oil repellency to a substrate.

When the novel composition is applied to a soiled substrate. e.g.. a carpet. the water and the detergent clean the substrate. The Lewis base temporarily maintains the composition above about pH 8 and thereby prevents premature formation of water-insoluble zinc or zirconium salts. As the cleaning operation continues. the Lewis base gradually loses its ability to maintain the composition pH above about 8. When the composition pH is reduced below about 8, the coordination complex provides zinc or zirconium ions which form solid, nontacky, hydrophobic, water-insoluble zinc or zirconium salts of the water-dispersible carboxyl-containing material. Surprisingly, these zinc or zirconium salts impart hydrophobicity to the substrate in the presence of the detergent residue. Below about pH 8 the fluorochemical is no longer water-dispersible and it is deposited on the substrate to impart water and oil repellency thereto.

DETAILED DESCRIPTION OF THE INVENTION The detergents or soaps which are useful in the novel compositions are those which dry to a nonoily, non tacky residue from an aqueous medium. Thus, solid detergents which leave a dry residue are desirable. Useful anionic detergents include alkali metal or ammonium salts of fatty acids (i.e., eight carbons or more), alcohol sulfates (or sulfonates), alcohol phosphates (or phosphonates), alkyl sulfonates, alkyl phosphates (or phosphonates), polyoxyalkylene alcohol sulfates (or sulfonates), polyoxyalkylene alkyl carboxylates, and poly oxyalkylene alcohol phosphates (or phosphonates).

Nonionic detergents, either by themselves or in conjunction with anionic detergents, can also be used in the novel compositions. When nonionic detergents are used, it is preferred that they be normally solid materials, or if not solid, that they be used in amounts less than about 2071 by weight of the total solids in the cleaning composition. Cationic detergents are not useful because they are not compatible with the other ingredients in the compositions.

The detergent must be water-dispersible at concentrations of at least 0.1 weight percent. The term water-dispersible" means that the detergent is either soluble, or otherwise stably dispersible, e.g., forms a colloidal suspension, in water at the desired concentration.

Useful water-dispersible organic carboxyl-containing materials which are capable of forming solid, hydrophobic, water-insoluble zinc and zirconium salts below about pH 8 are selected from the group consisting of:

i. water-dispersible mono-carboxylic acids having eight carbons or more, or alkali metal or ammonium salts thereof, and

ii. water-dispersible alkali metal or ammonium salts of polymers containing poly-carboxylic-acid functionality, the polymers having at least three carbons in the backbone chain per carboxyl group. Preferred waterdispersible monocarboxylic acids include fatty acids such as oleic, stearic, ricinoleic, palmitic, octanoic, tallow, linoleic, and iso-stearic. The alkali metal or ammonium salts of these acids are also useful.

Preferred water-dispersible organic carboxylcontaining materials are the ammonium salts of polymers containing polycarboxylic acid functionality. Such useful materials have an acid number of [-800. Representative of these materials are ammonium salts of styrene-maleic anhydride copolymers, safflower polyanhydrides, casein, and gelatin. Other useful materials include carboxylmethylccllulose. vinyl methyl cthermaleic anhydride copolymer. and polyacrylic acid copolymers.

The zinc and zirconium coordination complexes which are useful in the practice of this invention may be defined as those which are water-dispersible above about pH 8 and which provide zinc or zirconium ions (ill at or below about pH 8. The zinc or zirconium coordination complex preferably provides sufficient zinc or zirconium ions to combine with substantially all of the acidic radicals present in the composition. That is, as the composition becomes less basic (i.e., more acidic) zinc or zirconium ions are provided such that, at or below about pH 8, substantially all ofthe zinc or zirconium in the composition is capable of combining with substantially all of the acidic radicals in the composition.

Preferably, the ligand in the coordination complex ia ammonia although other ligands (such as morpholine) which are water-dispersible and have a maximum boiling point of about C. and a pK,, in the range of 3.()9.() are also quite useful. More preferable ligands have a pK, in the range of 3.0-6.0. Preferably, only volatile ligands are used, although a nonvolatile ligand (e.g., amino acid, alanine, glycine) which forms a solid. nontacky, water-insoluble zinc or zirconium salt below about pH 8 can be used in conjunction with a volatile ligand.

Lewis bases which are included in the composition are waterdispersible and are included in an amount sufficient to temporarily maintain the composition above about pH 8 when the composition is used on a substrate, Preferably, the Lewis base is volatile. The Lewis base can also function, if desired, as the ligand in the coordination complex. For example, ammonia can be used to both temporarily maintain the composition pH above 8 and also to furnish ligands for the zinc or zirconium coordination complex.

Useful Lewis bases include ammonia, morpholine and volatile alkylamines. Representative volatile alkylamines include triethylamine, propylamine, ethylamine, isopropylamine, isobutylamine, butylamine, ethanolamine, diethanolamine, methylethylamine, diethylaminoethanol, 2-amino-2-methylpropanol, etc.

In order to prepare cleaning compositions which can be extensively diluted (e.g., up to 40 times or more), a waterdispersible salt is included in the composition which, in combination with the Lewis base, forms abuffer system which is capable of maintaining desirable pH levels under these conditions of dilution. Prefera bly, the anions of these water-dispersible salts form zinc or zirconium salts below about pH 8 which are solid, nontacky, and nonhydroscopic. Examples of such water-dispersible salts include ammonium carbonate, ammonium alaninate, ammonium oxalate, ammonium formate, morpholinium carbonate, morpholinium formate, and ammonium acetate. The mole ratio of the water-dispersible salt to Lewis base is generally in the range of O. l:l to lOzl, and preferably in about l:l.

The fluorochemical compounds which can be used in the novel compositions are those which (u) are waterdispersible at or above about pH 8, (/7) have acid functionality, and (0] form zinc or zirconium salts which are capable of imparting water and oil repellency to a substrate. Preferably, such fluorochemical compounds have at least one fluoroaliphatic radical of three carbons or more and also have an acid group whose ionization constant is greater than I X It), Even more preferably, the ionization constant of the acid is less than about l X l0 but greater than I X 10*. Additionally, the fluorochemieal compound must form hydrophobic, water-insoluble zinc or zirconium salts below about pH 8 which are capable of imparting water and oil repellency to a substrate.

Structurally. the fluorochemieal compound is of the general formula (R,),.X(A)1,. where R, represents a fluoroaliphatic radical. X represents a linking group. A represents an acid group. a is an integer of l or more. and I) is an integer of l or morev R, is a fluorinated. preferably saturated. aliphatic radical of at least three carbon atoms. The skeletal carbon chain of the radical may be straight. branched. or if sufficiently large. cyclic. and may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms. A fully fluorinated group is preferred. but hydrogen or chlorine atoms may be present as substituents in the fluorinated aliphatic radi cal provided that not more than one atom of either is present in the radical for every two carbon atoms. and that the radical must at least contain a terminal perfluoroalkyl group. TerminaF in this connection refers to the position in the skeletal chain of the radical which is furthest removed from the backbone chain of the linking group. Preferably. the fluorinated aliphatic radical contains not more than carbon atoms because larger radicals result in inefficient use of the fluorine content. The term Rf has been widely used in the description of fluorochemical compounds. See. e.g.. U.S. Pat. Nos. 3.442.664, 3.510.455. 3,562.66. 3.574.791, 3.661.776.

The linking group X is polyvalent and is less electronegative than a CF group. The valence of X is a plus h. Representative linking groups include one or more of the following; alkylene (such as (CH. ,l,,. where n is l or more); arylene (such as phenylene); alkylidene; oxo; NR, where R is H or alkyl'. 50 CO; S; or any combination of these groups (eg, SO NR).

A is an acid group such as COOH;

The linking group and the acid group are selected such that the resulting fluorochemical compound is stable in the composition. is water-dispersible at or above about pH 8. and forms zinc or zirconium salts which are capable of imparting water and oil repellency to a substrate.

The novel compositions are normally concentrated and can be diluted with water (e.g.. up to 40 times or more) to provide cleaning and treating compositions which are more economical to use. In diluted form the compositions, for most economical use, preferably have the following concentrations of ingredients based on the total weight of the composition:

a. detergent: 0.ll.0 weight percent.

12. waterdispersible carboxyl-containing material:

0.2-2.0 weight percent.

-. coordination complex: an amount which provides sufficient zinc or Yirconium ions which are capable of combining with substantially all of the acidic radicals present in the composition (i.e.. at least one equivalent of metal ion for each acidic radical in the composition).

J. Lewis base: an amount sufficient to temporarily maintain the composition pH above about 8 when the Composition is applied to the substrate. and

e. fluorochemical compound: 0.05l.5 weight per cent. in all compositions. whether they be in concentrated or diluted form, the ingredients are normally present in the following weight ratios. with the amount of detergent present being designated as one part by weight:

u. detergent: 1 part by weight.

I. water-dispersible organic carboxyl-containing material: 0.1-6.5 parts. with 0.3-1 part being preferred.

c. coordination complex: an amount which provides sufficient zinc or zirconium ions which are capable of combining with substantially all of the acidic radicals present in the composition (i.e., at least one equivalent of metal ion for each acidic radical in the composition),

d. Lewis base: an amount sufficient to temporarily maintain the composition above about pH 8 when the composition is exposed to the atmosphere under conditions of use. and

e. fluorochemical compound; up to L5 parts. with 0.2-0.5 part being preferred for economic reasons.

The following examples are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention. Unless otherwise indicated. the term *parts means parts by weight.

Cleaning compositions within the scope of the invention can be prepared according to the following exemplary procedures.

EXAMPLE 1 First. a master batch ofa buffer system and a zinc coordination complex is prepared by mixing together the following ingredients in a closed container at room temperature:

l NH LCD 80 parts Cone. ammonia (28V: hl) parts Zn() 2.0 parts Water (distilled) 440 parts Next. a master batch of a water dispersion or solution of styrene-maleic anhydride copolymer (SM/X". commercially available from ARCO Chemical Co.) is prepared as follows: l2 parts of SMA (molecular weight l600) is added to 66 parts of water and the mixture is heated to C. with stirring for about I hour, after which 16 parts of Butyl Cellosolve"* is added with stirring. Then 0.5-l part of concentrated ammonia is added to the heated mixture to assist the solvation of the SMA." After the SMA is dissolved or stably dispersed. a sufficient amount of water is added to bring the total weight of the solution to 100 parts.

*Butyl Cellosolve is a tradcnamc of Union Carbide for the monobutyl ether of ethylene glycol,

A master batch of a water dispersion or solution of gelatin is prepared as follows: 8 parts of gelatin (Velvatex." a tradname of Swift Company) is added to parts of water which is then heated so as to dissolve the gelatin. Then 4 parts of concentrated ammonia are added to the solution followed by the addition of 4 parts of Butyl Cellosolve. Sufficient water is then added to bring the total weight of the solution to parts.

A typical water-dilutable cleaning composition is then prepared by adding together the following ingredients:

37 parts of the buffer and coordination complex 25 parts of the SMA master batch 25 parts of the gelatin master batch 10 parts of Richinol RS 1300 (a tradename of Richardson Co. for ammonium dodecanoxypolyethyleneoxy-ethyl sulfate) 50 parts of water 5 For cleaning carpets and upholstery this composition is diluted up to about five times the original weight with water.

EXAMPLES 2 27 It) tions is in the range of 9 to 10.5, wherein the tradenames used are defined as follows:

Richinol RS 1300" a tradename of Richardson TABLE I 8 Company for ammonium alcohol ether sulfate (60% active) Richonate SXS a tradename of Richardson Company for sodium xylene sulfonate active) Alipal (IO-426 a tradename of Antara Chemicals for an ammonium salt of a sulfate ester of an alkylphenoxy poly(ethyleneoxy) ethanol Richinol A" a trudename of Richardson Company for sodium lauryl sulfate (30% active) Richinol AM" a tradenamc of Richardson Chemical Company for ammonium lauryl sulfate (3271 active) Pluronic F68" a tradename of Wyandotte Chemicals Corporation for a copolymer of hydrophobic polyoxypropylene and hydrophilic polyoxyethylcne (mol. wt. 8750) SMA 1000" a tradename of Arco Chemical Company for styrene-maleic anhydride copolymer (mol. wt. 1600, acid number 480) SPA 230"a tradename of Pacific Vegetable Oil Corp. for maleinized safflower oils CLEANING AND TREATING COMPOSITIONS (i H l .I K I. M

"Richinol RS I300" Riuhonate SXS" -'Alipal (O-436" Richinol A-- Richinol AM" Pluronic Fhs" "SMA I000 Gelatin Casein SPA 230 Zinc oleale Iiut \l (ellosolvc" (one Ammonia Ammonium ('arhonale 0,60 3,00 IILbU 2.66

INGREDIENTS (PAR'I S BY WEIGH'I'I "Riehinol RS I" Richonale "Alipal (O-43h" Richinol A" Pluronie l es" SMA loot) (ielatin ('asein "SPA 230 Zinc oleute 3.00 loo Mm 21m ranges from 1 (poor oil repcllency) to 8 (excellent oil repellency). A rating of 2 or higher is acceptable.

Water repellcncy is tested by placing small droplets of water on the treated fabric surface and then observing for wetting of the surface. The rating scale is described at the bottom of Table ll. Water: isopropanol repcllency is tested according to the same manner as water repclleney. using \vater:isopropanol 1811:2(1) droplets.

TABLE l-CLEANING AND TREATING COMPOSITIONS-Continued INGREDIENTS N O P Q R S T U V W X Y Z (PARTS BY WElUHT) n Cellvwlw" 7.1111 13110 5.1111 1.411 2.1111 7.6111 13.1111 13.1111 11.1111 5.011 5.1111 9.1111 5.1111

Cone. Ammonia 11.50 28.00 11.711 (.111 1.911 111.1111 111.1111 111.1111 111.1111 3.711 7.115 7.1111 11.511

Ammonium 10.00 15.00 11.1111 11.1111 12.511 13.1111 13.1111 13.1111 4.93 1.33 Carbonate Zn las Z110) 5.011 sis ".911 1.511 3.17 3.311 3.311 3.311 2.25 1.23 3 33 s 511 Beta-alanine I lit) 1: 1 zHs) 4.211 4.311

CH,COOH 1C.. .1 -1N1C2H.1 3.511 3.1111 1.511 1 CH,COO),Zn C,.F ,SO.,N(C,H,,)CH,CH. O P QH 2.1111 (v.40 3.211 11.611 1.211 11.1111

ll 0 (C,.F,,SO,N(C:H,)CH2CH,-O),=P-OH I) O CF.|(CF )CF(CF;)n(i-NHCH,COOH

O n=25 CTFUCOONH4 (CHMCOOH): Water lulill Weight (parts) lZtl 350 l5l| I llltl lfil) Zlll) Zllt) 150 l5!) I51) lit) ll- EXAMPLE 28 TABLE ll 30 The cleaning compositions shown in Table I were Repcllenct each tested for water and oil repellency according to (leaning Composition 011* watt-r WaterzlPA 1111112111 the following procedure. A 1 F c 1 Several he1ge colored nylon carpet swatches. cut B (j from the same carpet, 15 ounce pile/square yard) are C j g first shampooed with a conventional commercial wet E Q u shampoo and allowed to dry. The carpet swatches are P 5 E (i then vacuum cleaned (4-6 passes) and tested for water 3 i and oil repellency. When oil and water droplets are 1 p p placed on the carpet swatches at this point. there is ini B S stant penetration and. thus. no repellency. L I; Z F Samples of each of the diluted cleaning compositions M 4 F P from Table I are applied to separate carpet swatches g w1th a brush or shampooer 1n the amount of 50 grams P 5 t (1 of diluted cleaning composition for each square foot of g 2 carpet. The cleaning compositions are allowed to dry 5 :1 E G and then the carpet swatches are vacuum cleaned. (lt I I J A I had previously been determined that grams ol eleanv 3 ing composition per square foot of carpet was sufficient Q 2 g for good cleaning of a heavily soiled carpet). l j; In Table ll there are compiled the results of various 7. 4 (1 P repellcncy tests. Oil repcllency is tested using the Hy- Th h, h I h H ,l

v A. ll. If l t. DUI "\I' K C pfLil UT 11. YL'\I ancc. drocarbon Reslstance Test (AAT (C l ll'l-l9h6T). p Wmmmm, Briefly. this test comprises placing drops of Standard l" "i lr ldelayed pcnetralim1.1.c. lc tlian l minute) i I x g v I (i (imul 11111 penetmhon lnr .11 least H1 minutes) tcht l SCI-e5 h.\dr0curhun5 with l l\ccllc111 11111 netting 117 'hlhfll'kllllll! I'or .11 least one hour) varying surface tensions) on the treated fabric surface and then observing for wetting of the surface by the 1 EXAMPl F 29 drops. lhe o|l repellcncy ratmg increases as the ab1l1t v of the fabric to resist wetting increases. The rating scale Several soiling tests were conducted in order to compare several of the novel cleaning compositions of the invention with conventional shampoo compositions.

A 30 gram sample of each shampoo and cleaning composition was used to clean individual beige nylon carpet swatches (9 inches square and cut from the same carpet). The carpet swatches were then dried. vacuum cleaned. and subjected to a 20 minute artificial soiling cycle. Al'ter soiling. the swatches were vacuum cleaned before reflectance readings were taken.

Subsequent soiling cycles were as follows: Each carpet swatch was then cleaned again with 30 grams of the respective shampoo or cleaning composition used previously on that swatch. After drying. the carpet swatches were vacuumed. resoiled for 20 minutes, vacuum cleaned, and then reflectance readings were again taken.

The result of the soiling tests are reported in Table III.

The artificial soiling test comprises (a) securing carpet swatches to the inside walls of a cylinder which contains lUl) small ceramic ball mill cylinders and a soiling formulation. and (b) rotating the cylinder at 42 revolutions per minute for 20 minutes. The cylinder is l3 /s inches high and has an inside diameter of 9% inches. The carpet swatches are ordinarily secured to the inside walls of the cylinder with double-coated pressuresensitive adhesive. The small ceramic ball mill cylinders are three-fourths inch by three-fourths inch in size and weigh about 23 grams.

The common soiling formulation used in the soiling test comprises:

Peat Moss 70 parts Gray Portland Cement ('l \pc l I 30 parts Silica gel [IOU mesh! 30 parts (lay 30 parts Sodium chloride [about St! mesh) 7 parts Gclatin 7 parts Carbon black 23 parts Rcd iron oxide 1 part Stcaric acid 3.2 parts Olcic acid 3.2 parts Pcanut oil 6 parts Lanolin 2 parts TABLE IV Photovolt Readings lst soiling 2nd Soiling 3rd Soiling (leaner ('yclc (yclc (yclc D (from Table ll 56 Sr 57 E (from Table l) 52 54 5 "Grace Lee" 47 45 43 Although it is preferred to use the compositions of the invention for cleaning and treating textile substrates. e.g.. and upholstery. these compositions also have utility for cleaning and treating various other sub stances. c.g.. metal surfaces. plastered surfaces, or ceramic surfaces. It will also be recognized that the novel compositions can be used solely for imparting waterand oil-repellent properties to a substrate by omitting the detergent and/or the organic acid from the formulation. it will also be recognized that a novel cleaning and treating composition can be obtained, which is capable of imparting water repellency to a substrate. by omitting the fluorochemical from the formulation.

In order to increase the adhesion of the insoluble zinc salts to the textile substrate, and to improve the dura bility of the treatment. a binder can also be included in the compositions of the invention. Preferably. such a binder comprises polar. water-soluble. high molecular weight resins. for example, useful binders include polyvinylpyrrolidone. polyvinylalcohol and natural gums. Binders can be used in amounts up to about 20% by weight of the total solid residue which is deposited on the treated substrate.

1 claim:

1. A containerstable. water-dilutable. alkaline cleaning composition capable of removing soil and stains from a substrate and imparting water and oil repellency and stain resistance to such substrate. the composition consisting essentially of in an aqueous medium:

a. one part by weight of at least one water-dispersible The higher thc reading the cleaner (hi: carpet Bissell Carpet Shampoo is a tradename of Bissell. Inc. Blue Lustre is a tradename of Earl Grissmer Co.. Inc. Grace Lee is a tradcname of Grace Lee Products. Duoway duoway" is a tradename of Solarine Co.

EXAMPLE 30 Soiling tests similar to those described in Example 29 were conducted on acrylic carpet swatches. The results are compiled in Table IV.

detergent which is capable of drying to a nonoily.

nontacky residue,

b. up to about 6.5 parts by weight of at least one ater-dispersil'ile organic carboxyLcont-aining material selected from the group consisting of:

i. water-dispersiblc monocarboxylic acids having eight carbons or more. or alkali metal or ammo' nium salts thereof. and

ii. water-dispersiblc alkali metal or ammonium salts of polymers containing poly-carboxylicacid functionality. said polymers having at least three carbons in the backbone chain per carboxyl group;

said carboxyl-containing material being free of fluoroaliphatic radicals and being capable offorming solid. hydrophobic. water-insoluble zinc and Zirconium salts below about pH 8.

'. at least one water-dispersible Lewis base present in an amount sufficient to temporarily maintain said composition above about pH 8 when said composition is exposed to the atmosphere under conditions of use. said Lewis base being selected from the group consisting of ammonia. morpholine. and volatile alkylamines.

d. at least one line or zirconium coordination complcx which is water-dispersible above about pH 8 and which provides sufficient zinc or zirzonium ions below about pH 8 which are capable of combining with substantially all of the acidic radicals present in said composition, and

e. up to about l ,5 parts by weight of at least one fluo rochemical compound having acid functionality. said fluorochemical compound having the formula: (R,) ,,-X( A),,. where R; is a fluoroaliphatic radical. a is an integer of l or more. X is a linking group having a valence of a plush and being less electronegative than a -CF:-- group. A is an acid group. and I; is an integer of l or more. said fluorochemical compound being capable of imparting water and oil repellency to a substrate.

2. A cleaning composition in accordance with claim 1 wherein said Lewis base comprises ammonia.

3. A container-stable. watendilutable. alkaline cleaning composition capable of removing soil and stains from a substrate and imparting water and oil repellency and stain resistance to such substrate. the composition consisting essentially of in an aqueous medium:

a. one part by weight of at least one water-dispersible detergent which is capable of drying to a nonoily. nontacky residue.

b. up to about 5 parts by weight of at least one waterdispersible organic carboxyl-containing material selected from the group consisting of:

i. water-dispersible mono-carboxylic acids having eight carbons or more. or alkali metal or ammonium salts thereof. and

ii. water-dispersible alkali metal or ammonium salts of polymers containing polycarboxylic-acid functionality. said polymers having at least 3 carbons in the backbone chain per carboxyl group;

said carboxyl-containing material being free of fluoroaliphatic radicals and being capable of forming solid. hydrophobic. water-insoluble Zinc and zirconium salts below about pH 8.

c. at least one watendispersible Lewis base and at least one water-dispersible salt which. in combination with said Lewis base. forms a buffer system capable of only temporarily maintaining said composition above about pH 8 when said composition is exposed to the atmosphere under conditions of Lise. said Lewis base being selected from the group consisting of ammonia. morpholinc. and volatile alkylamines.

at least one zinc or Yirconium coordination complex which is natendispersible above about pH 8 and which provides sufficient rinc or zirconium ions below about pH 8 which are capable of com bining with substantially all of the acidic radicals present in said composition; and

c. up to about L5 parts by weight of at least one fluorochemical compound having acid functionality. said fluorochemical compound having the formula: (R, ),,-X( AJ,,. where R, is a fluoroaliphatic radical. u is an integer of l or more, X is a linking group having a valence of a plus I) and being less electronegative than a CF. group. A is an acid group. and l) is an integer of l or more. said fluorochemical compound being capable of imparting water and oil repellency to a substrate.

4. A cleaning composition in accordance with claim 3 wherein said Lewis base comprises ammonia.

5. A cleaning composition in accordance with claim 4 wherein said water-dispersible salt comprises ammonium carbonate.

6. A container-stable. water-dilutable. alkaline cleaning composition capable of removing soil and stains from a substrate and imparting water repellency to such substrate. the composition consisting essentially of in an aqueous medium:

av one part by weight of at least one water-dispersible detergent which is capable of drying to a nonoily. nontacky residue.

b. up to about 6.5 parts by weight of at least one watcr-dispcrsible organic carboxyl-containing material selected from the group consisting of:

i. water-dispersible mono-carboxylic acids having eight carbons or more. or alkali metal or ammonium salts thereof. and

ii. water-dispersible alkali metal or ammonium salts of polymers containing poly-carboxylic-acid functionality, said polymers having at least three carbons in the backbone chain per carboxyl group;

said carboxyl-containing material being free of fluoroaliphatic radicals and being capable of forming solid. hydrophobic. water-insoluble zinc and zirconium salts below about pH 8.

c. a Lewis base present in an amount sufticient to temporarily maintain said composition above about pH 8 when said composition is exposed to the atmosphere under conditions of use. said Lewis base being selected from the group consisting of ammonia. morpholine. and volatile alkylamines.

d. at least one zinc or zirconium coordination complex which is water-dispersible above about pH 8 and which provided sufficient zinc or zirconium ions below about pH 8 which are capable of com bining with substantially all of the acidic radicals present in said composition.

7. A cleaning composition in accordance with claim 1 wherein said carboxyLcontaining material is an ammonium salt of a styrenemaleic anhydride copolymer and wherein said fluorochemical compound comprises an organic acid having an ionization constant less than about l X 10" but greater than I X 10 8. A cleaning composition in accordance with claim 3 wherein said carboxyl-containing material is an ammonium salt of a styrene-maleic anhydride copolymer and wherein said fluorochemical compound comprises an organic acid having an ionization constant less than about I X 10"" but greater than I X lU".

9. A process for removing soil and stains from a sub- 1 5 l6 strate and imparting water and oil repellency and stain h. substantially drying said substrate so that the pH resistance to such substrate. the process comprising the of said composition is reduced below about 8, steps of: thereby forming a solid residue on said substrate,

a. contacting said substrate with an effective cleaning and amount of the cleaning composition of claim l, 5 c. vacuum cleaning said substrate.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. I 3,901,727 DATED August 26, 1975 |NVENTOR(S) BASIL L. LOUDAS It is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below;

Col. 2, line 2, after "composition", first occurrence, add above Col. 5, line 66, the sentence In all compositions...parts by weight: should start a new paragraph.

Col. 7 & 8, Table I, "C F COONH should read Col. 8, line 6, "Alipal (IO- 426" should read "Alipal CO- l36" H II Col. 11, line 61, Duoway""duoway" should read Inc. "Duoway" Col. 1, line 51, "provided" should read provides Col. 12, line 29, "for" should read For Signed and Scaled this A ttes t:

RUTH C. MASON C MARSHALL D AMPS!!! Officer ANN Commissioner ufPa rents and Trademarks 

1. A CONTAINER-STABLE, WATER-DILUTABLE, ALKALINE CLEANING COMPOSITION CAPABLE OF REMOVING SOIL AND STAINS FROM A SUBSTRATE AND IMPARTING WATER AND OIL REPELLENCY AND STAIN RESISTANCE TO SUCH SUBSTRATE, THE COMPOSITION CONSISTING ESSENTIALLY OF IN AN AQUEOUS MEDIUM: A. ONE PART BY WEIGHT OF AT LEAST ONE WATER-DISPERSIBLE DETERGENT WHICH IS CAPABLE OF DRYING TO A NONOILY, NONTACKY RESIDUE, B. UP TO ABOUT 6.5 PARTS BY WEIGHT OF AT LEAST ONE WATER-DISPERSIBLE ORGANIC CARBOXYL-CONTAINING MATERIAL SELECTED FROM THE GROUP CONSISTING OF: I. WATER-DISPERSIBLE MONO-CARBOXYLIC ACIDS HAVING EIGHT CARBONS OR MORE, OR ALKALI METAL OR AMMONIUM SALTS THEREOF, AND II. WATER-DISPERSIBLE ALKALI METAL OR AMMONIUM SALTS OF POLYMERS CONTAINING POLY-CARBOXYLIC-ACID FUNCTIONALITY, SAID POLYMERS HVING AT LEAST THREE CARBONS IN THE BACKBONE CHAIN PER CARBOXYL GROUP, SAID CARBOXYL-CONTAINING MATERIAL BEING FREE OF FLUOROALIPHATIC RADICALS AND BEING CAPABLE OF FORMING SOLID, HYDROPHOBIC, WATER-INSOLUBLE ZINC AND ZIRCONIUM SALTS BELOW ABOUT PH 8, C. AT LEAST ONE WATER-DISPERSIBLE LEWIS BASE PRESENT IN AN AMOUNT SUFFICIENT TO TEMPORARILY MAINTAIN SAID COMPOSITION ABOVE ABOUT PH 8 WHEN SAID COMPOSITION IS EXPOSED TO THE ATMOSPHERE UNDER CONDITIONS OF USE, SAID LEWIS BASE BEING SELECTED FROM THE GROUP CONSISTING OF AMMONIA, MORPHOLINE, AND VOLATILE ALKYLAMINES, D. AT LEAST ONE ZINC OR ZIRCONIUM COORDINATION COMPLEX WHICH IS WATER-DISPERSIBLE ABOVE ABOUT PH 8 AND WHICH PROVIDES SUFFICIENT ZINC OR ZIRZONIUM IONS BELOW ABOUT PH 8 WHICH ARE CAPABLE OF COMBINING WITH SUBSTANTIALLY ALL OF THE ACIDIC RADICALS PRESENT IN SAID COMPOSITION, AND E. UP TO ABOUT 1.5 PARTS BY WEIGHT OF AT LEAST ONE FLUOROCHEMICAL COMPOUND HAVING ACID FUNCTIONALITY, SAID FLUOROCHEMICAL COMPOUND HAVING THE FORMULA: (RF) A-X-(A)B, WHERE RF IS A FLUPROALUPHATIC RADICAL, A IS AN INTEGER OF 1 OR MORE, X IS A LINKING GROUP HAVING A VALENCE OF A PLUS B AND BEING LESS ELECTRONEGATIVE THAN A -CF2GROUP, A IS AN ACID GROUP, AND B IS AN INTEGER OF 1 OR MORE, SAID FLUOROCHEMICAL COMPOUND BEING CAPABLE OF IMPARTING WATER AND OIL REPELLENCY TO A SUBSTRATE.
 2. A cleaning composition in accordance with claim 1 wherein said Lewis base comprises ammonia.
 3. A container-stable, water-dilutable, alkaline cleaning composition capable of removing soil and stains from a substrate and imparting water and oil repellency and stain resistance to such substrate, the composition consisting essentially of in an aqueous medium: a. one part by weight of at least one water-dispersible detergent which is capable of drying to a nonoily, nontacky residue, b. up to about 5 parts by weight of at least one water-dispersible organic carboxyl-containing material selected from the group consisting of: i. water-dispersible mono-carboxylic acids having eight carbons or more, or alkali metal or ammonium salts thereof, and ii. water-dispersible alkali metal or ammonium salts of polymers containing poly-carboxylic-acid functionality, said polymers having at least 3 carbons in the backbone chain per carboxyl group; said carboxyl-containing material being free of fluoroaliphatic radicals and being capable of forming solid, hydrophobic, water-insoluble zinc and zirconium salts below about pH 8, c. at least one water-dispersible Lewis base and at least one water-dispersible salt which, in combination with said Lewis base, forms a buffer system capable of only temporarily maintaining said composition above about pH 8 when said composition is exposed to the atmosphere under conditions of use, said Lewis base being selected from the group consisting of ammonia, morpholine, and volatile alkylamines, d. at least one zinc or zirconium coordination complex which is water-dispersible above about pH 8 and which provides sufficient zinc or zirconium ions below about pH 8 which are capable of combining with substantially all of the acidic radicals present in said composition; and e. up to about 1.5 parts by weight of at least one fluorochemical compound having acid functionality, said fluorochemical compound having the formula: (Rf)a-X-(A)b, where Rf is a fluoroaliphatic radical, a is an integer of 1 or more, X is a linking group having a valence of a plus b and being less electronegative than a -CF2- group, A is an acid group, and b is an integer of 1 or more, said fluorochemical compound being capable of imparting water and oil repellency to a substrate.
 4. A cleaning composition in accordance with claim 3 wherein said Lewis base comprises ammonia.
 5. A cleaning composition in accordance with claim 4 wherein said water-dispersible salt comprises ammonium carbonate.
 6. A container-stable, water-dilutable, alkaline cleaning composition capable of removing soil and stains from a substrate and imparting water repellency to such substrate, the composition consisting essentially of in an aqueous medium: a. one part by weight of at least one water-dispersible detergent which is capable of drying to a nonoily, nontacky residue, b. up to about 6.5 parts by weight of at least one water-dispersible organic carboxyl-containing material selected from the group consisting of: i. water-dispersible mono-carboxylic acids having eight carbons or more, or alkali metal or ammonium salts thereof, and ii. water-dispersible alkali metal or ammonium salts of polymers containing poly-carboxylic-acid functionality, said polymers having at least three carbons in the backbone chain per carboxyl group; said carboxyl-containing material being free of fluoroaliphatic radicals and being capable of forming solid, hydrophobic, water-insoluble zinc and zirconium salts below about pH 8, c. a Lewis base present in an amount sufficient to temporarily maintain said composition above about pH 8 when said composition is exposed to the atmosphere under conditions of use, said Lewis base being selected from the group consisting of ammonia, morpholine, and volatile alkylamines, d. at least one zinc or zirconium coordination complex which is water-dispersible above about pH 8 and which provided sufficient zinc or zirconium ions below about pH 8 which are capable of combining with substantially all of the acidic radicals present in said composition.
 7. A cleaning composition in accordance with claim 1 wherein said carboxyl-containing material is an ammonium salt of a styrene-maleic anhydride copolymer and wherein said fluorochemical compound comprises an organic acid having an ionization constant less than about 1 X 10 3 but greater than 1 X 10
 9. 8. A cleaning composition in accordance with claim 3 wherein said carboxyl-containing material is an ammonium salt of a styrene-maleic anhydride copolymer and wherein said fluorochemical compound comprises an organic acid having an ionization constant less than about 1 X 10 3 but greater Than 1 X 10
 9. 9. A process for removing soil and stains from a substrate and imparting water and oil repellency and stain resistance to such substrate, the process comprising the steps of: a. contacting said substrate with an effective cleaning amount of the cleaning composition of claim 1, b. substantially drying said substrate so that the pH of said composition is reduced below about 8, thereby forming a solid residue on said substrate, and c. vacuum cleaning said substrate. 